Singlet oxygen-based photocatalytic oxygenation reactions have emerged as an efficient technology to synthesize value-added organic molecules. Among organic substrates, bio-sourced molecules such as aminoacids or terpenes have a promising forecast as synthetic building blocks. A pseudo first-order kinetic study for the photocatalytic oxygenation of natural amino acid (L)-methionine was carried out in a macroscopic batch reactor. Various parameters were studied, including the effect of the photosensitizer (Rose Bengal, RB) concentration, the intensity of the light and the O2 flow in terms of apparent kinetic constants and space-time yields. The identification of important limiting parameters as pressure, gas flow or light efficiency during the photocatalytic oxygenation of methionine allowed its transition from macroscopic batch reactor to continuous-flow microreactor. [less ▲]

in Journal of Photochemistry and Photobiology A : Chemistry (2018), 350

Zinc was coupled with titanium dioxide using different methods. SiO2 and Zn-SiO2 doped TiO2 films, on the one hand, and Zn doped TiO2 on the other hand, have been produced using controlled sol-gel ... [more ▼]

Zinc was coupled with titanium dioxide using different methods. SiO2 and Zn-SiO2 doped TiO2 films, on the one hand, and Zn doped TiO2 on the other hand, have been produced using controlled sol-gel processes by alcoholic, cogelation and aqueous ways. From these syntheses, films were deposited on soda lime glass. These samples were compared to ZnO samples but also to bilayer samples constituting one layer of TiO2 and one layer of ZnO. The physico-chemical properties of the films were characterized by grazing-incidence X-ray diffraction, profilometry and UV-Vis absorption analyses. The photocatalytic activity has been evaluated from the degradation of methylene blue under UV-A light, from the degradation of p-nitrophenol under visible light and from the degradation of H2O2 under halogen light (UV-A + visible light). Superhydrophilicity was evaluated from contact angle measurement after UV exposition and also from hysteresis effects. Finally, a haze measurement was performed to evaluate the impact of the coating on the aesthetic property of the coated glass. Aqueous films have better photocatalytic activity and superhydrophilicity than samples from alcoholic synthesis. The crystallization of the sample appears to be one key factor: alcoholic films required calcination to ensure the crystallization of TiO2, but the alkali migration from the glass support prevents this crystallisation, while aqueous synthesis promotes crystallized particles at low temperatures without alkali interference. It appears that the relative activity from one sample to another depends on the nature of the illumination and on the nature of the molecule to be degraded. Nevertheless, the sample with ZnO layer deposited on first TiO2 layer (ZnO 500 Alc/TiO2 100 AQ) composite is found to be the best sample, maintaining a high hydrophilicity similar to TiO2 and a good activity. [less ▲]

The objective of this study is to determine operational processes for advanced oxidative treatment of waste waters contaminated with Pharmaceutical Products (PPs). The aim is to validate a physico ... [more ▼]

The objective of this study is to determine operational processes for advanced oxidative treatment of waste waters contaminated with Pharmaceutical Products (PPs). The aim is to validate a physico-chemical process combining ozonation and photocatalysis and that has to be placed downstream a classical biological treatment in existing waste water treatment plants (WWTP - domestic, industrial or hospital). [less ▲]

Highly efficient and chemoselective singlet oxygen oxidation of unprotected methionine was performed in water using a continuous mesofluidic reactor. Sustainable process engineering and conditions were ... [more ▼]

Highly efficient and chemoselective singlet oxygen oxidation of unprotected methionine was performed in water using a continuous mesofluidic reactor. Sustainable process engineering and conditions were combined to maximize process efficiency and atom-economy, with virtually no waste generation and safe operating conditions. Three water soluble metal-free photosensitizers (Rose Bengal, Methylene Blue, and tetrakis(4-carboxyphenyl)porphyrin) were assessed. The best results were obtained with Rose Bengal (0.1 mol%) at room temperature under white light irradiation and a slight excess of oxygen. Process and reaction parameters were monitored in real-time with in-line NMR. Other classical organic substrates (alpha-terpinene and citronellol) were oxidized under similar conditions with excellent performances. [less ▲]

During the 20th century, degradable aliphatic polyesters have undergone fast and dynamic developments. Nowadays, these materials can be found in several areas of human activities. Originally there have ... [more ▼]

During the 20th century, degradable aliphatic polyesters have undergone fast and dynamic developments. Nowadays, these materials can be found in several areas of human activities. Originally there have been first designed for the pharmaceutical and medical fields, in particular in surgery and for drug delivery systems. In these domains, polymers are synthesized according to a batch procedure due to the low capacity needed. This work is dedicated to the optimization of a continuous synthesis of pharmaceutical grade polyesters (e.g. poly-L-lactide, PLLA) by reactive extrusion using a twin screws extruder. This equipment presents several advantages compared to batch reactor such as: absence of solvent, high degree of mixing, easiness of scale-up, and rapid continuous synthesis. PLLA synthesis by reactive extrusion has been performed adopting a co-rotating twin-screws extruder (diameter=11 mm and L/D ratio=40). A highly active catalyst must be used to reach the target conversion due to the limited residence time. Tin octoate, approved by US Food and Drugs Administration, has been used alone as catalyst considering a catalyst / monomer molar ratio of 1/5000. A polyethylene glycol has been adopted as initiator. 1H.NMR and size exclusion chromatography (SEC) have been adopted to monitor the conversion rate of the monomer and to analyse the mean molecular weights and the corresponding polydispersity. Static mechanical tests have also carried out to assess the influence of residual monomer within the polymer. Our optimization study has highlighted that the main challenging aspects were the control of the reaction atmosphere and of the residence time. In the first case, even presence in trace water can competitively initiate the polymerization, but also promote hydrolysis. In order to reach a high monomer conversion (≥ 99 %), the residence time has to be well controlled and extended. This latter parameter is particularly affected by the screw configuration and the use of the protic initiator. In particular, the screw configuration was based on previous studies dedicated to the synthesis of polyesters by reactive extrusion [1, 2]. After synthesis, post-processing step was realized in order to reduce the monomer residue. Once optimized we have succeeded to reach in a reproducible way high molecular weight PLLA (typically in a range of 50 to 100 KDa) with a high monomer conversion (>96 %) on a time scale of some minutes. Post-polymerization has successfully decreased the residual monomer below 1%. In conclusion, this work provides a continuous and robust process to synthesize pharmaceutical grade PLLA by reactive extrusion. References : [less ▲]

A process has been developed to enable the large scale production of pure TiO2 films deposited on 316L stainless steel in order to get an easy-to-clean surface. This large scale process requires an easy ... [more ▼]

A process has been developed to enable the large scale production of pure TiO2 films deposited on 316L stainless steel in order to get an easy-to-clean surface. This large scale process requires an easy aqueous sol-gel procedure for the synthesis of the TiO2 sol. This synthesis has been simplified to facilitate the extrapolation towards an industrial scale. Results of TEM, photocatalytic properties, film hydrophilicity, and texture obtained with the simplified aqueous sol-gel synthesis (IsoP-TiO2 synthesis) show similar properties to those obtained with the standard aqueous sol-gel synthesis of TiO2 (HAc-TiO2 synthesis) developed previously. Only X-Ray Diffraction patterns showed differences, with the presence of anatase-brookite phases in IsoP-TiO2 synthesis while anatase phase only was observed in HAc-TiO2 synthesis. Both the aqueous sol-gel synthesis of pure TiO2 and the film deposition on steel by roll-coating have been successfully extrapolated to a larger scale. The photocatalytic activity and the hydrophilicity of the film were found to be unchanged when compared to films produced at a laboratory scale, thus validating the production of an efficient easy-to-clean material. Although some problems are still to be solved, this study is a hopeful first step in the development of a large scale process for self-cleaning steel production. [less ▲]

An aqueous sol-gel process, previously developed for producing undoped and Cu2+, Ni2+, Zn2+ or Pb2+ doped TiO2 photocatalysts with remarkably high photocatalytic activity without requiring any calcination ... [more ▼]

An aqueous sol-gel process, previously developed for producing undoped and Cu2+, Ni2+, Zn2+ or Pb2+ doped TiO2 photocatalysts with remarkably high photocatalytic activity without requiring any calcination step, has been adapted to produce Fe3+, Cr3+, La3+ or Eu3+ single-doped TiO2 photocatalysts as well as La3+-Fe3+ and Eu3+-Fe3+ co-doped TiO2 catalysts. The physicochemical properties of the obtained catalysts have been characterized using a suite of complementary techniques, including ICP-AES, XRD, UV-Vis spectroscopy, nitrogen adsorption-desorption and Fe-57 Mössbauer. The active crystalline phase is obtained without requiring any calcination step and all the different catalysts are composed of nanocrystallites of anatase with a size of 6-7 nm and a high specific surface area varying from 181 to 298 m² g-1. In this study, the effect of the NO3:Ti(IV) mole ratio used to induce the peptisation reaction during the synthesis has been studied and the results revealed that this ratio can influence significantly the textural properties of the resulting catalyst. A screening of the photocatalytic activity of the undoped and Fe3+, Cr3+, La3+ or Eu3+ single-doped and co-doped photocatalysts has been performed by evaluating the degradation of 4-nitrophenol under UV-Visible light (330 nm < λ < 800 nm). This study suggests that the photocatalytic activity is significantly influenced by the dopant nature and content with an optimal dopant content being observed in the case of Fe3+ or La3+ single-doped as well as in the case of La3+-Fe3+ and Eu3+-Fe3+ co-doped catalysts. In the case of Cr3+ single-doped catalysts, a detrimental effect of the dopant on the photocatalytic degradation of 4-nitrophenol has been observed while no significant influence of the dopant has been detected in the case of Eu3+ single-doped catalysts. The role of the different dopants in modulating the photocatalytic activity is discussed. [less ▲]

Development of photochemistry in macroscopic batch reaction vessels is hampered due to inherent limitations: light penetration remains superficial, resulting in inhomogeneous irradiation and hence to side ... [more ▼]

Development of photochemistry in macroscopic batch reaction vessels is hampered due to inherent limitations: light penetration remains superficial, resulting in inhomogeneous irradiation and hence to side-reactions or product degradation due to overexposure. The recent implementation of photochemical processes in microreactors under continuous-flow conditions appeared to be much more powerful than its batch analogue in terms of irradiation efficiency and light penetration. Furthermore, the fine control of residence time ensures an accurate control of the irradiation time, avoiding side-reactions and degradation. The photooxidation of (L)-methionine with singlet oxygen using Rose Bengal as a sensitizer was successfully implemented in a microreactor setup and led to total and selective conversion into methionine sulfoxide, an important building block for the organic synthesis of peptides or functionalized amino acid. The reaction was performed in 2 min while the same reaction in batch took 2h. [less ▲]

Development of photochemistry in macroscopic batch reaction vessels is hampered due to inherent limitations: light penetration remains superficial, resulting in inhomogeneous irradiation and hence to side ... [more ▼]

Development of photochemistry in macroscopic batch reaction vessels is hampered due to inherent limitations: light penetration remains superficial, resulting in inhomogeneous irradiation and hence to side-reactions or product degradation due to overexposure. The recent implementation of photochemical processes in microreactors under continuous-flow conditions appeared to be much more powerful than its batch analogue in terms of irradiation efficiency and light penetration. Furthermore, the fine control of residence time ensures an accurate control of the irradiation time, avoiding side-reactions and degradation. The photooxidation of (L)-methionine with singlet oxygen using Rose Bengal as a sensitizer was successfully implemented in a microreactor setup and led to total and selective conversion into methionine sulfoxide, an important building block for the organic synthesis of peptides or functionalized amino acid. The reaction was performed in 20 min while the same reaction in batch took 2h. [less ▲]

In this paper, an easy aqueous sol-gel synthesis developed previously by Mahy et al. [J. Sol-Gel Sci. Technol. (2016)] is adapted to produce highly active TiO2 catalysts doped with Fe3+, Ag+, Cu2+, Zn2+, Cr3+, Al3+, Mn2+, and Co2+ ions and Pt metallic nanoparticles. Samples are characterized by inductively coupled plasma–atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), Mössbauer spectroscopy, transmission electron microscopy (TEM), nitrogen adsorption–desorption measurements and diffuse reflectance spectroscopy measurements. Results show that the samples are composed of anatase-brookite TiO2 nanoparticles with a spherical shape and mean diameter of around 5-8 nm and a surface area of between about 150 - 250 m2 g-1. In each doped sample, the dopant is present in the form added during the synthesis, given that the sample has not undergone any particular treatment. Photoactivity tests show improvement in catalyst activity for Fe3+, Ag+, Cu2+, Zn2+, and Al3+ ion and Pt metallic nanoparticle dopants, while a decrease of activity is obtained for Cr3+, Mn2+ and Co2+ ion dopants. For some dopants, the activity of TiO2 doped with metallic ions and synthesized from the aqueous sol-gel process is equal or superior to the activity of the commercial photocatalyst Degussa P25. Some mechanisms are proposed to explain these modifications of activity with doping. Furthermore, cost comparison at laboratory scale showed that Zn and Cu nitrate salt dopings are clearly less expensive for a halogen light (UV/visible) or low energy light enhanced catalyst and may be considered for industrial applications. Using this method, a large scale Zn-doped TiO2 photocatalyst is synthesized with properties homologous to the lab-scale product. Results show that the aqueous sol-gel synthesis developed previously can be easily adapted for doping in order to produce an up-scalable synthesis. [less ▲]

The thermochemical method called “biomass gasification” is generating emphatic interest for the production of bio-Syngas (CO + H2) since this process presents the advantage of being renewable without ... [more ▼]

The thermochemical method called “biomass gasification” is generating emphatic interest for the production of bio-Syngas (CO + H2) since this process presents the advantage of being renewable without emitting CO2. However, in practical applications, there are still some technical problems due to high tars concentration in the outlet gas which can condensate and clog the pipes. Many studies have highlighted the fact that the tar elimination via catalytic reforming seem to be the more practical and economical solution. The required properties of the catalysts are determined by its location: inside the reactor (primary catalyst) or outside of the reactor (secondary catalyst). Primary catalysts are generally robust, non-toxic, cheap and they are almost uniquely destined to fluidized bed reactors. Secondary catalysts can be used at the exit of both fluidized and fixed bed reactors. They are characterized by a tailored mesoporous shape, a controlled active site dispersion and an adapted elemental composition [1]. In this work , we decided to focus on designing materials for secondary catalytic applications, i.e. working at relatively low temperature (~650°C) with no mechanical stress. The supports were made of γ-Al2O3 synthesized via an easy Sol-Gel method. During their synthesis, these supports were doped with 10%wt of nickel and various combinations of metallic dopants (Co, Cu, Fe, Mn, Mo) in the aim of enhancing their catalytic activities and lifetime. [less ▲]

In this work, a global process has been developed to produce at a large scale pure TiO2 films deposited on steel in order to get an easy-to-clean surface. This large scale process implies an easy aqueous ... [more ▼]

In this work, a global process has been developed to produce at a large scale pure TiO2 films deposited on steel in order to get an easy-to-clean surface. This large scale process implies an easy aqueous sol-gel process for the synthesis of the TiO2 sol. This synthesis [1] has been simplified to make easier the extrapolation towards an industrial scale. Results of TEM, photocatalytic properties, film hydrophilicity, and texture obtained with the simplified aqueous sol-gel synthesis (IsoP-TiO2 synthesis) show similar properties than those obtained with the standard aqueous sol-gel synthesis of TiO2 developed previously (HAc-TiO2 synthesis [2]). Only XRD patterns were slightly different with the presence of anatase-brookite phases in IsoP-TiO2 synthesis while anatase phase only was observed in HAc-TiO2 synthesis. Both the aqueous sol-gel synthesis of pure TiO2 and the film deposition on steel by roll-coating have been successfully extrapolated to a larger scale. Indeed, the deposition was done on a pilot line, the steel substrate is 25 cm width, and the band length is 800 m. The coating was deposited at line speed ranging from 30 to 120 m.min-1.The photocatalytic activity and the hydrophilicity of the film were found to be unchanged compared to the films produced at a laboratory scale, thus validating the production of an efficient easy-to-clean material. Even if some problems have still to be solved, this study is a hopeful first step in the development of a large scale process for self-cleaning steel production. [1] S. Mahshid, M. Askari, M.S. Ghamsari, J. Mater. Process. Technol. 189 (2007) 296–300 [2] C.M. Malengreaux, S. Douven, D. Poelman, B. Heinrichs, J.R. Bartlett, J. Sol-Gel Sci. Technol. 71 (2014) 557–570 [less ▲]